Azo dyestuffs



United States Patent 3,135,732 AZG DYESTUFFS Kari-Heinz Schiindehiitte, Leverlrusen, Horst Nickel,

Cologne-Stemmheim, Karl-Heinz Schmidt, Cologne- Flittard, and Fritz Sucltfiill, Leverkusen, Germany, assignors to l arheni ahril-zen Bayer Aktiengesellschaft, Leverhusen, Germany, a corporation of Germany No Drawing. Filed Han. 12, E50, Ser. No. 1,881 Claims priority, application Germany Ian. 3.4, 1%9

4 Claims. ('61. 269-457) The present invention relates to valuable azo dyestufits; more particularly it relates to azo dyestutis of the formula SI 0 3H In this formula R means the residue of an aromatic diazo compound, X stands for hydrogen or a sulfonic acid group, R denotes a carbocyclic nucleus bearing the azo bridge wd Y in the p-position to each other, Y means one of the bridge members -N N,

and terephthaloylamino, and R stands for the residue of a carbocyclic or heterocyclic component.

The new dyestuffs are obtainable by coupling 2,5-diammo-naphthalene-4,8-dior -8-monosultonic acid with an aromatic diazo compound in o-position to the positioned amino group, triazolizing the dyestufi obtained, further diazotising, coupling with a carbocyclic amino compound in p-position to the amino group and transforming in the dyestuif obtained the end-positioned amino group into a bridge member -N:N,

HN-COCH=CHCONH-, a 2,4-triazinyl- [1,3,51-aminoor terephthaloylarnino radical.

Aromatic diazo compounds suitable for the process for the first coupling are accessible by diazotising aro- 'matic amino or aminoazo compounds for example,

ice

in the dyestutr' oi the general formula wherein X, R and R have the same significance as mentioned above, into a bridge member Y of the above-' indicated meaning can, for example, be carried out by:

(a) Acylation of (II) with polyfunctional acylation agents such as phosgene, cyanuric chloride, fumaric acid dichloride or terephthalic acid dichloride, whereby symetrical dyestufis or, in the case where a second amino compound R of diiierent structure is used, unsymmetri-- cal dyestuffs are obtained;

(b) Further diazotization of the compound (II), coupling with a coupling component in o-position to a hydroxyl group and, if desired, transformation of the ohydroxyazo dyestufi into a metal complex compound, preferably copper complex compound; or

(0) Further diazotization ot the amino group-containing compound (ll), coupling with a coupling component in o-position to an amino group and transformation of the o-aminoazo dyestull into a triazole compound;

(d) Further diazotization of the amino group-containing compound (II), coupling with a carbocyclic amine in p-position to the amino group, further diazotisation and coupling with a coupling component in o-position to an amino group, and transformation of the o-aminoazo dyestuff thus obtained into a triazole compound.

The reaction of the azo compounds of the Formula H with polyfunctional acyiation agents (process ((1)) is carried out according to known processes in aqueous SOilltion in the presence of acid-binding agents such as sodium carbonate. In the production of unsymmetrical dyestuffs, colored or uncolored compounds can be intro duced as the second amino component R Coupl ng components suitable for the further diazotisation, coupling and, it desire subsequent metal complex formation (process (b)) which couple in the 0- position to a hydroxyl group are for example l-hydroxy- 4-rnethylbenzene, p-hydroxybenZyl-sulfonic acid, 1-hydroxynaphthalene-4-sultonic acid, Z-hydroxynaphthalene- 3,6-disulfonic acid, l-phenyl-3-methyl-5-pyrazolone as well as azo group-containing coupling components such as the monoazo dyestuif from diazotised l-chloro-Z- amino-S-benzenesulfonyl hydroxynaphthalene-7-sulfonic acid and 2-hydroxynaphthalene-3,ddisulfonic acid (saponified) among others.

The metal free dyestutls obtained according to proo ess (Z1) correspond to the formula N (HI) other, R represents the residue of a coupling component which may contain further azo groups and Z is a group forming a metal complex such as a hydroxyl or carboxy group, or a substituent being transtormable into such a group, such as a lower alkoxy group, Z and 0H standing in o-position, to the external azo bridge.

The metallisation of these dyestuffs may becarried out according to known processes. If Z in o-position to the external azo group represents a hydroxy or carboxyl group the complex formation occurs immediately by the action of the metal salt concerned, for example a nickel or copper salt. If Z stands for an alkoxy group or a halogen substituent, this can be replaced for example with Fehlings solution with formation of a complex bound hydroxyl group. Finally, hydrogen atoms or sulfonic acid groups (Z) standing in o-position to the azo group can be transformed into copper complex bound hydroxyl groups according to the processes of oxidising coppering e.g. according to German patent specifications 807,289, 889,196, 893,699 and 1,006,098.

By coupling with coupling components in o-position to an amino group and subsequent triazolisation according to the process dyestuifs result of the general formula diazotised and coupled with an amino group-containing carbocyclic compound dyestuffs of the followinggeueral structure are producible wherein R, X and R have the above significance and R and R stand for carbocyclic nuclei, R having the azo bridges and R having the azo bridge and triazole group- ,ing in p-position to each other.

The same dyestufis as are obtained by the processes (a), (b), (c) or (d)'may be produced when starting from 2-acylamino-5-aminonaphthalene-4,8-dior -8-monosulfonic acid and, after the first coupling in the 6-position and triazolisation, splitting oh? the acyl group and otherwise proceeding in the same manner as described above.

Further embodiments of producing the new dyestuffs consist in varying the sequence of the various process steps. Thus, for example, 2-aminoor 2-acylamino-5- aminonaphthalene-4,8-dior -8-monosulfonic acid can be coupled with the diazo compound sition (if desired after hydrolysis of the acylamino group) for example in Weakly acid medium, then coupling with the carbocyclic amino compound R --NH or in p-position to the amino group, then carrying out the triazolisation at the residue R and finally transforming the amino group in the residue R or can first be produced and this reacted with a second,

amine component.

In the presence of metal complex forming substituents, for example in dyestuffs of the Formula HI, the metallising of the dyestuffs can be carried out in various phases of the production process. The metal-containing dyestuifs can furthermore be de-metallized by known processes and the dyeings after-treated on the fibre with metal salts.

Preferred metal complex forming agents are copper, nickel, iron, manganese, chromium and cobalt salts.

In the case where the residues R and R in the Formula I possess groups which are capable of further reactions for example nitro groups, which combine with nitro groups of a second component with reductive formation of azo or azoxy groups, or amino groups which can be reacted with monoor polyfunctional acyl-ating agents, such reactions can be interposed as intermediate steps or carried out after the conclusion of the above-described process.

The new azo dyestuffs are suitable, inter alia, for dyeing vegetable fibres, especially cotton and viscose. The dyeings on these fibres are distinguished by good fastness properties especially good light-fastness and wetfastness. The following examples are given for the purpose of illustrating the invention without, however, limiting it thereto.

' Example 1 The solution of 31.8 parts by weight (0.1 mol) of 2,5-diamino naphthalene-4,8-disulphonic acid in 1000 parts by volume of water is treated with 25 parts by weight 'of sodium acetate and then with the diazo compound from 17.3 parts by Weighe of l-aminobenzene-4-sulphonic acid at 0 C. After the coupling is completed the reaction solution is brought by addition of hydrochloric acid to a pH of 1, the dyestuif separated with 150 parts by weight of sodium chloride and isolated by filtering off with suction.

The paste obtained is dissolved in 1000 parts by volume of hot water and treated with a solution of 56 parts by Weight of crystalline copper sulphate in parts by volume of water and 130 parts by volume of 25% aqueous ammoma. about 3 hours until triazolisation is terminated. After cooling to room temperature the mixture is acidified with hydrochloric acid, 200 parts by Weight of sodium chloride are added and the aminotriazole is isolated.

0.1 mol of the aminotriazole compound are dissolved in weakly soda alkaline in 900 parts by volume of water, treated with 69 parts by volume of a 10% sodium nitrite solution and stirred at 15 C. into a mixture of 42 parts by volume of'hydrochloric acid (d. 1.14) and 50 parts by volume water. After the diazotisation is completed a solution of 10.7 parts by weight of 1-amino-3-methylbenzene in 50 parts by volume of water. and 15 parts by volume of hydrochloric acid (d. 1.14) are added at 0-3 C. and finally parts by volume of a 20% sodium acetate solution are added. After coupling is completed the reaction product is isolated while acid to Congo red.

The compound obtained is dissolved weakly soda alka line in 2100 parts by volume water and diazotised by treating with 69 parts by volume of a 10% sodium nitrite solution at 40 C. After diazotisation is completed the Stirring is then continued at 90-95 C. for' isolated diazonium salt iscoupled at 03 C. with the neutral solution of 22.3 parts by weight of Z-amino-naphthalene-6-sulphonic acid in 600 parts by volume of water and the amino diazo dyestufi subsequently separated.

The paste obtained is dissolved in 1400 parts by volume of hot water, treated with the solution of 56 parts by weight of crystalline copper sulphate in 140 parts by volume of water and 130 parts by volume of a 25% aqueous ammonia and boiled until completion of triazolisation. After separation of the cuprous oxide by filtrationoptionally with the addition of animal charcoalthe dyestufi is separated out of a filtrate with sodium chloride and isolated. The dyestutr" obtained corresponds in a form of the free acid to the formula After drying it represents a brown powder which dissolves in water with a yellow colour and dyes cotton in yellow shades with very good tastness properties. 7 The substitution of 1-aminobenzene-4-sulphonic acid by equivalent quantities of the dehydrotbiotoluidinedisulphom'c acid, dehydrothiotoluidine-sulphonic acid, l-aminonaphthalene-4-sulphonic acid, l-aminonaphthalene-S-sulphonic acid, and Z-aminonaphthalene6-sulphonic acid leads to dyestuffs which likewise dye cotton in yellow shades.

in an analogous manner to that described in Example 1, 0.1 mol of 2,S-diaminonaphthalene-8-sulphonic acid is coupled with diazotised l-aminobenzene-3-sulphonic acid, triazolised, coupled with 1-amino-3-methylbenzene and then with Z-aminonaphthalene-6-sulphonic acid and transformed into the triazole. A dyestufr is thus obtained which dyes cotton in yellow shades.

oiN

Example 2 27.7 parts by weight (0.1 mol) of 4-aminoazobenzene- 4'-sulphonic acid are diazotised and as described in Ex- If this triazole compound is diazotised according to a process analogous to that described in Example 1, coupled with 1-amino-3-methylbenzene, again diazotised, coupled with 2-aminonaphthalene-6-sulphnic acid and subsequently triazolised, a dyestuti is obtained which likewise dyes cotton in yellow shades.

If in this example 4-aminoazobenzene-4'-sulfonic acid is substituted by an equivalent quantity of naphthalene- 4,8-disulfonic acid-2,4'-azo-Y-mino-T-methylbenzene or l-amino-2-methoxy-6-methyl-azobenzene-4'-sulfonic acid or by the coupling product from diazotised naphthalene- 6,8-disulfonic acid-2,4'-azo-l'-amino-3'-methylbenzene and l-amino-3-methylbenzene and the process then 01- lower as described above, a dyestufi is obtained which likewise dyes cotton with yellow to orange shades.

If instead of 1-amino-3 -ruethylbenzene there are used as middle components aminobenzene, l-amino-Lmethoxy- 6-methylbenzene, l-aminonaphthalene or l-arninonaphthalene--sulfonic acid dyestufis are obtained which dye I sc n which is obtained dyes cotton in yellow shades.

Example 4 0.1 mol of the amino triazole produced according to the method of the first paragraph in Example 2 are coupled with the equivalent quantity of 1-amino-3-rnethylbenzene; the amino a0 compound obtained is then transformed with phosgene in the usual manner into the symmetrical urea of the following formula:

sonar HOaS-C N-N 7 The dyestuff dyes cotton in gold yellow s'had'es. The dyeings are distinguished by good fastness properties.

I Example 0.1 mol-of the first-mentioned aminotriazol compound from Example 1 are diazotised and coupled at pH 3-4 with the equivalent quantity of 2-ethoxy-l-aminonaphthalene-6-sulfonic acid. After isolation the 'aminoazo cornpound is further diazotised in 1000 parts by volume of water at 20 C. and coupled in bicarbonate-alkaline me- 10 dium with addition of 100 ml. of pyridine with 2-hydroxynaphthalene-3,6-disulfonic acid. The azo dyestuft obtained is transformed by methods known as such into the 'copper complex compound, which is a dark powder,

which dissolves in water with a green color and dyes cotton in green shades. It corresponds to the formula SIO H O-Cu-O If as end component Z-hydroxynaphthalene-6-sulfonic acid or l-hydroxynaphthalene-4-sulfonic acid is used dyestufis are likewise obtained which dye cotton in green shades.

The dyestufis may be de-coppered according to usual methods. and then again metallized either on a substrate or in substance with, for instance, copper-, nickelor chromium salts.

If the amino triazole compound in this example is replaced by the aminotriazole compound SIO3H I SO H and one proceeds as above, a dyestufi? is obtained which dyes cotton in green shades with good light fastness.

If the 2-ethoxy-1-aminonaphthalene-6-sulphonic acid is replaced by 1-aminonaphthalene-6-sulfonic acid, the

aminoazo dyestuif thus obtained coupled with 2-hydroxynaphthalene-3,6-disulphonic acid and then transformed into the copper complex dyestufi according to the methods of oxidising coppering, the above described dyestutf (V) is likewise obtained.

If 2-ethoxy-1-aminonaphthalene-6-sulfonic acid is replaced in this example by Z-aminobenzene-l-carboxylic SOsH ' Exam pl'e .6

v If 0.1 mol of the aminoazo dyestutf of the formula SIOQH is diazotised as usual, coupled with 2,5-diaminonaphthalene-4,8-disulphonic acid at pH 4-5, triazolisedand according to the instructions of Example 2 first coupled with l-amino-S-methylbenzene and 'then with Z-aminonaphthalene-6-sulphonic acid and finally triazolised, a

dyestuff is obtained which dyes cotton in brown shades.

' If 0.1 mol of the aminoazo dyestuif of the formula H038 o-ou-,o

I I I HOaS NHz N= NEN are coupled as usualwith 1-amino-3-methyl benzene. The aminodisazo dyestuif obtained is further diazotised at room temperature, coupled with 2-aminonaphthalene- 6-sulphonic acid and transformed into the triazole compound. The dyestuif is obtained of the formula I SO H acid and the aminoazo dyestufi obtained is diazotised and coupled in soda-alkaline medium with l-hydroxynaphthalene-4-sulfonic acid a dyestuff is obtained which dyes cotton in brown shades.

which dyes wool in orange coloured shades.

If the first mentioned triazole component of Example 2 is used in this example a dyestuflf is, obtained which dyes cotton in orange coloured shades.

wherein R is the residue of a diazo compound selected from the group consisting of the benzene, azobenzene,

naphthalene and dehydrothiotoluidine series; R stands for a divalent radical selected from the group consisting of the phenylene, naphthylene and phenylazophenyl series, R bearing the two -N-- groups in para-position to I @bhN-O-Nd $11,

l I (in N s N l s 3 as N-N each other; R is the residue of an amine of the naphthalene series and bearing the triazole group on adjacent carbon atoms; X is a member selected from the group consisting of H and SO H; R containing at least one substituent selected from the group consisting of H, SO H, COOH, and OCH R containing at least one substituent selected from the group consisting of H, CH OCH SO H, COOH, OC H and Br; and R containing at least one substituent selected from the group consisting of hydrogen, COOH and 80 1-1.

2. The dyestufl which in the free acid state corresponds to the formula SIOs 3. The dyestufi which in the free acid state corresponds to the formula SOQH 4. The dyestutl which in the free acid state corresponds to the formula References Cited in the file of this patent UNITED STATES PATENTS 2,176,521 Bonhote et al. Oct. 17, 1939 2,212,816 Schultis et a1 Aug. 27, 1940 2,390,480 West Dec. 4, 1945 2,788,345 Hanhart Apr. 9, 1957 2,795,577 Feeman June 11, 1957 2,817,659 Bossard et a1 Dec. 24, 1957 2,932,636 Suckfull et al. Apr. 12, 1960 

1. A COMPOUND OF THE FORMULA 